CN110923755A - Surface anti-oxidation process for lithium-ion battery copper foil - Google Patents
Surface anti-oxidation process for lithium-ion battery copper foil Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 71
- 239000011889 copper foil Substances 0.000 title claims abstract description 67
- 230000008569 process Effects 0.000 title claims abstract description 67
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 230000003064 anti-oxidating effect Effects 0.000 title claims abstract description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title description 20
- 229910001416 lithium ion Inorganic materials 0.000 title description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 47
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 47
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 34
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 28
- 239000008103 glucose Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 3
- 230000002265 prevention Effects 0.000 claims description 35
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052804 chromium Inorganic materials 0.000 abstract description 28
- 239000011651 chromium Substances 0.000 abstract description 28
- 238000009713 electroplating Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001514 detection method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012797 qualification Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0657—Conducting rolls
Abstract
The invention discloses a surface anti-oxidation process of a lithium electro-copper foil, which is carried out in an anti-oxidation tank and comprises the following steps: (1) preparing an initial anti-oxidation liquid: the initial anti-oxidation liquid is formed by mixing chromic anhydride, glucose and water, wherein the mass ratio of chromic anhydride to glucose is chromic anhydride: glucose powder =1: 3-1: 5, and the concentration of glucose in the initial anti-oxidation liquid is 1.5-2.7 g/L; (2) controlling anti-oxidation electroplating parameters: after the lithium electrolytic copper foil is immersed in the initial anti-oxidation liquid, the following parameters are controlled until the end: the circulation flow of the anti-oxidation liquid is 1.8-2.5 m3The temperature is 32-34 ℃, the pH is 5-6, and the concentration of hexavalent chromium is 0.5-0.7 g/L. The lithium electrolytic copper foil treated by the process has oxidation resistanceGood and low chromium content on one side.
Description
Technical Field
The invention relates to the field of electrochemistry, and particularly relates to an anti-oxidation process for the surface of a lithium-ion electro-copper foil
Background
The electrolytic copper foil is a core material of the lithium ion battery cathode, and the quality of the copper foil has important influence on the cathode manufacturing process and the lithium battery performance. Lithium-ion electro-copper foils are generally produced by electrolytic processes. After the electrolytic bath is rolled down, the surface of the copper foil is oxidized if it is stored for a long time, and the oxidation of the copper foil is accelerated by high temperature, moisture, etc. Therefore, the surface of the copper foil is subjected to an oxidation preventing treatment. In the prior art, an anti-oxidation film mainly containing zinc and chromium is plated on two sides of a copper foil through a chemical method or an electrolytic method, so that the copper foil is isolated from air, and the purpose of oxidation resistance is achieved. The chromium-containing anti-oxidation process is simple, the raw materials are low in price, and the generated chromium-containing anti-oxidation film has a good air isolation effect and strong high-temperature resistance. Therefore, at present, it is most common to subject the surface of the copper foil to oxidation-preventing treatment using hexavalent chromium (chromic acid or a salt thereof). However, hexavalent chromium has strong carcinogenicity and causes serious harm to human bodies and the environment. Therefore, there is a need for a new environment-friendly oxidation preventing process for lithium-ion-battery copper foil.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a novel anti-oxidation treatment process for the surface of a lithium-ion electro-deposited copper foil. The process is environment-friendly; after the surface anti-oxidation treatment process is adopted, the surface of the lithium electro-copper foil has good oxidation resistance and extremely low chromium plating amount (the chromium plating amount on one surface is less than 3 mg/m)2）。
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a surface oxidation prevention process for a lithium electro-copper foil, which is carried out in an oxidation prevention tank, comprises the following steps:
(1) preparation of initial anti-oxidation liquid
The initial anti-oxidation liquid is formed by mixing chromic anhydride, glucose and water, wherein the mass ratio of chromic anhydride to glucose is chromic anhydride: glucose powder =1: 3-1: 5, and the concentration of glucose in the initial anti-oxidation liquid is 1.5-2.7 g/L;
(2) controlling anti-oxidation electroplating parameters;
after the lithium electrolytic copper foil is immersed in the initial anti-oxidation liquid, the following parameters are controlled until the end:
the circulation flow of the anti-oxidation liquid is 1.8-2.5 m3The temperature is 32-34 ℃, the pH is 5-6, and the concentration of hexavalent chromium is 0.5-0.7 g/L.
Preferably, in the initial oxidation preventing liquid, the mass ratio of chromic anhydride to glucose is chromic anhydride to glucose =1: 3.2.
Preferably, the concentration of glucose in the initial oxidation preventing liquid is 2.0 g/L.
Preferably, the circulation flow rate of the anti-oxidation liquid is 2m3/h。
Preferably, the pH of the oxidation preventing liquid is controlled with potassium hydroxide or sodium hydroxide.
More preferably, the pH value of the anti-oxidation liquid is controlled by a potassium hydroxide aqueous solution with the mass percentage concentration of 10% -15%.
Preferably, the current for the oxidation-resistant electroplating is 4-6A.
The invention also aims to provide the lithium-ion electro-copper foil treated by the surface anti-oxidation process.
In the present specification, the "water" is tap water from which chloride ions have been removed, such as pure water produced by an electrolytic process (electrolytic pure water), unless otherwise specified.
By the surface anti-oxidation treatment process of the lithium electro-copper foil, the lithium electro-copper foil can reach the standard requirement on oxidation resistance at 150 ℃ for 15 min. In addition, the chromium content of the surface of the lithium-ion battery copper foil treated by the traditional anti-oxidation process is generally 5.8 mg/m2Left and right. The concentration of chromic anhydride in the initial anti-oxidation liquid is only about 0.6 g/L, and the chromium content on the surface of the copper foil is less than 3mg/m after the treatment by the process provided by the invention2And the surface oxidation resistance of the lithium electro-copper foil is obviously lower than that of the lithium electro-copper foil treated by the traditional surface oxidation resistance process. Therefore, the lithium-ion electro-copper foil surface oxidation prevention process can obviously reduce the consumption of chromic anhydride on one hand, and improves the safety of the copper foil in the using process due to the reduction of the chromium content on the surface of the lithium-ion electro-copper foil on the other hand, thereby reducing the health of operators and reducing the pollution to the health of the operatorsThe environment is damaged, thereby being beneficial to the environmental protection and the continuous development of production enterprises.
Drawings
The present invention will be described in detail with reference to the accompanying drawings.
Fig. 1 is a schematic view showing an apparatus for performing oxidation-preventing treatment of the surface of an electrolytic copper foil, wherein:
1: a titanium roller; 2: a peeling roller; 3: copper foil; 4: passivating the conductive roller; 5: an oven; 6: a transition roll; 7: a wind-up roll: 8: an anode tank; 9: an anti-oxidation tank.
Detailed Description
The invention is further illustrated by the following examples. It is to be understood that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The instruments and devices used in the following examples are those commonly used in the art unless otherwise specified. Reagents, raw materials and the like used in the examples are commercially available if not specifically mentioned.
Example 1 surface oxidation prevention process for lithium electro-copper foil
In this example, the lithium electrolytic copper foil was produced by an electrolytic method, electrolytic copper formation and oxidation prevention treatment were continuously performed, and the entire production process was performed in a medium electrolytic system. The medium-sized electrolysis system is schematically shown in FIG. 1. An electrolyte circulating system in an anode tank 8 is 30 cubic meters, a cathode roller is a titanium roller 1 and is installed in the anode tank 8, under the condition of electrifying (with an impressed current of 25 KA), copper foil generated through electrolysis is wound on the titanium roller 1, lithium electrolytic copper foil enters an anti-oxidation tank 9 through a stripping roller 2 and a passivation conductive roller 4 (with a passivation current of 5A and a voltage of 4.8V) in a reverse stripping sequence at the running speed of 5.2m/min, and is dried through an oven 5 and finally passes through a transition roller 6 and a winding roller 7, and the copper foil with a chromium coating is produced after surface anti-oxidation treatment.
The electrolyte in the anode tank is an acidic solution containing copper ions and additives, and is prepared according to a conventional method in the field. Namely: electrolytic copper or copper wire rod is used as raw material (copper content is more than 99.9%) and is chemically reacted with sulfuric acid, etc., and necessary additive is added to prepare the solution.
The initial anti-oxidation liquid comprises the following components in parts by weight:
according to the mass ratio of chromic anhydride to glucose, the chromic anhydride is as follows: and (2) weighing 0.6846kg of chromic anhydride and 2.1kg of glucose powder, transferring the chromic anhydride and the glucose powder into a preparation tank with the volume of 1050L, filling electrolytic pure water, and uniformly mixing to ensure that the concentration of the glucose in the initial anti-oxidation liquid is 2.0g/L, thereby obtaining the initial anti-oxidation liquid.
Transferring the initial anti-oxidation liquid into an anti-oxidation tank 9, transferring the electrolyte into an anode tank 8, switching on a power supply, wherein the impressed current of the titanium roller is 25KA, the impressed current of the passivated conductive roller (namely the current of the anti-oxidation electroplating) is 5A, and the voltage is 4.8V. Controlling the circulation flow of the anti-oxidation liquid to be 2m from the beginning of the lithium electrolytic copper foil entering the anti-oxidation tank3The temperature is 32-34 ℃, the concentration of hexavalent chromium is 0.5-0.7 g/L, and the pH value is kept to be 5-6 by 10% (w/w) potassium hydroxide aqueous solution until the production is finished.
The lithium electro-copper foil obtained by performing 100 times of pilot production according to the process is qualified in oxidation resistance at 150 ℃ for 10min (determined according to a SJT11483-2014 load collecting method, the testing condition is improved to be harsher at 150 ℃ for 10min from 140 ℃ for 15min specified by a standard), and the chromium content of a single surface is less than 3mg/m2. Now, randomly extracted 10 sets of data are shown in table 1.
Table 1 randomly extracted 10 groups of data
The data in table 1 show that the lithium electro-copper foil treated by the process of the present invention has excellent high temperature oxidation resistance and the single-sided chromium plating amount is maintained at a low level.
Embodiment 2 surface oxidation prevention process for lithium-ion battery copper foil
The oxidation prevention process for the surface of the lithium-ion-coated copper foil is carried out in the equipment in the embodiment 1, the process and the process are basically the same as those in the embodiment 1, and the difference is that the circulation flow of the oxidation prevention liquid is 1.8 m3/h。
The lithium electrolytic copper foil obtained by the process of the embodiment is qualified in oxidation resistance after being detected at 150 ℃ for 10min, and the content of chromium on the rough surface is 2.0-2.2 mg/m2The chromium content of the polished surface is 1.9-2.1 mg/m2。
Embodiment 3 surface oxidation prevention process for lithium-ion battery copper foil
The oxidation prevention process for the surface of the lithium-ion-coated copper foil is carried out in the equipment in the embodiment 1, the process and the process are basically the same as those in the embodiment 1, and the difference is that the circulation flow of the oxidation prevention liquid is 2.5 m3/h。
The lithium electrolytic copper foil obtained by the process of the embodiment is qualified in oxidation resistance after being detected at 150 ℃ for 10min, and the content of chromium on the rough surface is 2.5-2.8 mg/m2The chromium content of the polished surface is 2.2-2.6 mg/m2。
Comparative example 1 surface oxidation prevention process for lithium electrolytic copper foil
The surface oxidation prevention process for the lithium-ion-containing electro-deposited copper foil is carried out in the equipment in the embodiment 1, and the process are basically the same as those in the embodiment 1, except that in the initial oxidation prevention liquid, the mass ratio of chromic anhydride to glucose is that chromic anhydride to glucose =1:5.5, and the concentration of glucose in the initial oxidation prevention liquid is 2 g/L.
The oxidation resistance of the lithium electrolytic copper foil obtained by the process treatment of the comparative example is unstable after being detected at 150 ℃ for 10min, and the detection qualification rate cannot reach 100%; the chromium content of the smooth surface is 0.8-1.1 mg/m2The chromium content of the rough surface is 0.9-1.3 mg/m2。
Comparative example 2 surface oxidation prevention process for lithium electro-copper foil
The surface oxidation prevention process for the lithium-ion-containing electro-copper foil is carried out in the equipment in the embodiment 1, and the process are basically the same as those in the embodiment 1, except that in the initial oxidation prevention liquid, the mass ratio of chromic anhydride to glucose is that chromic anhydride to glucose =1:2, and the concentration of glucose in the initial oxidation prevention liquid is 2 g/L.
The oxidation resistance of the lithium electrolytic copper foil obtained by the process treatment of the comparative example is unstable after being detected at 150 ℃ for 10min, and the detection qualification rate cannot reach 100%; the chromium content of the smooth surface is 4.1-4.4 mg/m2, and the chromium content of the rough surface is 4.2-4.7 mg/m2。
Comparative example 3 surface oxidation prevention process for lithium electro-copper foil
The oxidation prevention process for the surface of the lithium-ion-coated copper foil is carried out in the equipment in the embodiment 1, the process and the process are basically the same as those in the embodiment 1, and the difference is that the circulation flow of the oxidation prevention liquid is 1.5m3/h。
The oxidation resistance of the lithium electrolytic copper foil obtained by the process treatment of the comparative example is unstable after being detected at 150 ℃ for 10min, and the detection qualification rate cannot reach 100%; the chromium content of the smooth surface is 1.2-1.5 mg/m2The chromium content of the rough surface is 1.3-1.7 mg/m2。
Comparative example 4 surface oxidation prevention process for lithium electro-copper foil
The oxidation prevention process for the surface of the lithium-ion-coated copper foil is carried out in the equipment in the embodiment 1, the process and the process are basically the same as those in the embodiment 1, and the difference is that the circulation flow of the oxidation prevention liquid is 3.0 m3/h。
The oxidation resistance of the lithium electrolytic copper foil obtained by the process treatment of the comparative example is unstable after being detected at 150 ℃ for 10min, and the detection qualification rate cannot reach 100%; the chromium content of the smooth surface is 4.5-4.9 mg/m2The chromium content of the rough surface is 4.7-5.1 mg/m2。
Comparative example 5 surface oxidation prevention process for lithium electrolytic copper foil
The oxidation prevention process for the surface of the lithium-ion-coated copper foil is performed in the equipment in the embodiment 1, and the process are basically the same as those in the embodiment 1, except that the current for the oxidation prevention electroplating is 3A.
The lithium electrolytic copper foil obtained by the process treatment of the comparative example has unstable oxidation resistance after being detected at 150 ℃ for 10min, and can not reach the detection qualified rate100 percent; the chromium content of the smooth surface is 0.5-1.1 mg/m2The chromium content of the rough surface is 0.8-1.2 mg/m2。
Comparative example 6 surface oxidation prevention process for lithium electrolytic copper foil
The oxidation prevention process for the surface of the lithium-ion-coated copper foil is performed in the equipment in the embodiment 1, and the process are basically the same as those in the embodiment 1, except that the current for the oxidation prevention electroplating is 7A.
The oxidation resistance of the lithium electrolytic copper foil obtained by the process treatment of the comparative example is unstable after being detected at 150 ℃ for 10min, and the detection qualification rate cannot reach 100%; the chromium content of the smooth surface is 4.9-5.1 mg/m2The chromium content of the rough surface is 5.1-5.3 mg/m2。
Claims (8)
1. A surface oxidation prevention process for a lithium electro-copper foil, which is carried out in an oxidation prevention tank, comprises the following steps:
(1) preparation of initial anti-oxidation liquid
The initial anti-oxidation liquid is formed by mixing chromic anhydride, glucose and water, wherein the mass ratio of chromic anhydride to glucose is chromic anhydride: glucose powder =1: 3-1: 5, and the concentration of glucose in the initial anti-oxidation liquid is 1.5-2.7 g/L;
(2) oxidation resistant plating parameter control
After the lithium electrolytic copper foil is immersed in the initial anti-oxidation liquid, the following parameters are controlled until the end:
the circulation flow of the anti-oxidation liquid is 1.8-2.5 m3The temperature is 32-34 ℃, the pH is 5-6, and the concentration of hexavalent chromium is 0.5-0.7 g/L.
2. The surface oxidation preventing process according to claim 1, wherein a mass ratio of chromic anhydride to glucose in the initial oxidation preventing liquid is chromic anhydride to glucose =1: 3.2.
3. The surface oxidation preventing process according to claim 1 or 2, wherein a concentration of the glucose in the initial oxidation preventing liquid is 2.0 g/L.
4. A surface oxidation preventing process according to any one of claims 1 to 3, wherein a circulation flow rate of the oxidation preventing liquid is 2m3/h。
5. The surface oxidation preventing process according to claim 1, wherein the pH of the oxidation preventing liquid is controlled with potassium hydroxide or sodium hydroxide.
6. The surface oxidation prevention process as claimed in claim 5, wherein the pH of the oxidation prevention solution is controlled by a potassium hydroxide aqueous solution having a concentration of 10 to 15% by mass.
7. The surface oxidation preventing process according to claim 1, wherein the current for the oxidation preventing plating is 4 to 6A.
8. A lithium electrolytic copper foil treated by the surface oxidation preventing process according to any one of claims 1 to 7.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112921311A (en) * | 2021-01-25 | 2021-06-08 | 湖北中一科技股份有限公司 | Method for preventing end face of electrolytic copper foil from discoloring |
| CN114507851A (en) * | 2022-02-18 | 2022-05-17 | 梅州市威利邦电子科技有限公司 | Low-chromium washing-free anti-oxidation liquid for electrolytic copper foil for lithium ion battery and washing-free anti-oxidation process thereof |
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| GB2017154A (en) * | 1978-03-14 | 1979-10-03 | Centre Rech Metallurgique | Quenching and metal caoting metal strip |
| CN105386106A (en) * | 2015-11-25 | 2016-03-09 | 青海电子材料产业发展有限公司 | Lithium electric copper foil anti-oxidization liquid and anti-oxidization treatment technology |
| CN110424012A (en) * | 2019-08-12 | 2019-11-08 | 湖北中一科技股份有限公司 | A kind of electrolytic copper foil surface processing method |
| CN110438531A (en) * | 2019-08-12 | 2019-11-12 | 湖北中一科技股份有限公司 | A kind of extra thin copper foil preparation method and system applied to lithium battery |
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| CN112921311A (en) * | 2021-01-25 | 2021-06-08 | 湖北中一科技股份有限公司 | Method for preventing end face of electrolytic copper foil from discoloring |
| CN112921311B (en) * | 2021-01-25 | 2024-02-06 | 湖北中一科技股份有限公司 | Method for preventing electrolytic copper foil end face from changing color |
| CN114507851A (en) * | 2022-02-18 | 2022-05-17 | 梅州市威利邦电子科技有限公司 | Low-chromium washing-free anti-oxidation liquid for electrolytic copper foil for lithium ion battery and washing-free anti-oxidation process thereof |
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Denomination of invention: A surface anti oxidation process for lithium battery copper foil Effective date of registration: 20231226 Granted publication date: 20210730 Pledgee: Jiujiang Bank Co.,Ltd. Pledgor: JIUJIANG DEFU TECHNOLOGY Co.,Ltd. Registration number: Y2023980074569 |